JP2024505046A - curable composition - Google Patents

Abstract

TECHNICAL FIELD This application relates to resin compositions and uses thereof. The present application can provide a resin composition or a cured product thereof that exhibits high thermal conductivity and low adhesive strength to a predetermined adherend. Further, in the present application, the low adhesive strength can be achieved without using an adhesive strength adjusting component such as a plasticizer, or by minimizing the proportion of the adhesive strength adjusting component such as a plasticizer. The present application can also provide a product containing the curable composition or a cured product thereof.

Description

This application relates to curable compositions.

The importance of heat-dissipating materials is increasing as the number of electrical or electronic devices that require heat management, such as batteries, increases.
Various types of heat dissipation materials are known. As one of the conventional heat dissipating materials, a material in which a resin binder is filled with a heat dissipating filler is known (for example, Patent Document 1).

As the resin binder in the above-mentioned heat dissipating material, silicone resin, polyolefin resin, acrylic resin, or epoxy resin is usually used.
Heat dissipating materials are basically required to have excellent thermal conductivity, and additional functions are also required depending on the application. For example, some applications require heat dissipating materials to exhibit high thermal conductivity as well as low adhesion to certain adherends.

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For example, when it is necessary to replace parts that come into contact with the heat dissipation material within a product, or when it is necessary to change the position of the heat dissipation material during the process, the heat dissipation material needs to exhibit low adhesive strength. do.
Among known heat dissipating materials, materials exhibiting low adhesive strength include materials to which silicone resin is applied as a resin binder. However, silicone resins are relatively expensive. Furthermore, silicone resins contain components that can cause contact failure when applied to electronic/electrical products, so their uses are limited.

The polyurethane material used in Patent Document 1 can form a heat dissipating material with high thermal conductivity and has various other advantages, but it also exhibits high adhesive strength to most adherends. It is the material.
As a method for reducing the adhesive strength of materials that exhibit high adhesive strength, there is a method of blending a component known as a so-called plasticizer. However, plasticizers added in large amounts to control adhesive strength have problems such as impairing the inherent advantages of the material itself and leaching out during the use process.

Korean Patent Publication No. 2016-0105354

The present application aims to provide a curable composition. One object of the present application is for the curable composition or its cured product to exhibit high thermal conductivity while exhibiting low adhesive strength to a predetermined adherend. Further, the object of the present application includes achieving the low adhesive strength without using or minimizing the proportion of adhesive strength adjusting components such as plasticizers.
Another object of the present application is to provide a product containing the curable composition or a cured product thereof.

Among the physical properties mentioned in this specification, when the measurement temperature affects the results, unless otherwise specified, the physical properties are those measured at room temperature. The term ambient temperature refers to the natural temperature without heating or cooling, and usually means a temperature in the range of about 10°C to 30°C or a temperature on the order of about 23°C or about 25°C. Further, unless otherwise specified in this specification, the unit of temperature is °C.

Among the physical properties mentioned in this specification, when the measured pressure affects the results, unless otherwise specified, the physical properties are those measured at normal pressure. The term normal pressure refers to the natural pressure without pressurization or depressurization, and the range of about 700 mmHg to 800 mmHg is usually referred to as normal pressure.
TECHNICAL FIELD This application relates to resin compositions. The term resin composition refers to compositions that include components known in the art as resins or compositions that do not include resins, but that include components that can form resins, such as through a curing reaction.

Accordingly, the term resin or resin component as used herein includes not only components commonly known as resins, but also components capable of forming resins through curing and/or polymerization reactions.
The resin composition may be a curable composition.
When the resin composition of the present application is a curable resin composition, the resin composition may be a one-component or two-component resin composition. The term one-component resin composition refers to a resin composition in which the components that participate in curing are in physical contact with each other, and the term two-component resin composition refers to a resin composition that contains components that participate in curing. It can mean a resin composition in which at least a part of the resin composition is physically separated and contained.

When the resin composition of the present application is a curable resin composition, the resin composition may be a room temperature curable type, a heat curable type, an energy ray curable type, and/or a moisture curable type. The term cold curable refers to a resin composition in which the curing reaction can be initiated and/or proceeded at room temperature, and the term heat curable refers to a resin composition in which the curing reaction can be initiated and/or proceeded by the application of heat. The term energy ray curable refers to a resin composition in which the curing reaction can be initiated and/or progressed by irradiation with energy rays (e.g., ultraviolet rays, electron beams, etc.), and the term moisture curable refers to resin compositions in which the curing reaction can be initiated and/or proceeded by irradiation with energy rays (e.g., ultraviolet rays, electron beams, etc.). Refers to a resin composition that can be started and/or proceeded with.

The resin composition of the present application may be solvent-based or solvent-free. In consideration of application efficiency and environmental impact, it is appropriate to use a solvent-free type.
The resin composition of the present application may be a polyurethane composition. In such a case, the resin composition may contain polyurethane or a component capable of forming polyurethane.
The resin composition of the present application exhibits low adhesive strength to a specific adherend, or can form a cured product capable of exhibiting low adhesive strength.

Such a resin composition of the present application may be a polyurethane composition. Polyurethane is known as an adhesive material that can exhibit excellent adhesion to various adherends. Therefore, as a method for a polyurethane composition to exhibit low adhesive strength to an adherend, a method of introducing a component that reduces adhesive strength, such as a plasticizer, is usually used. Application of components such as plasticizers can reduce the adhesive strength of polyurethane materials, but these components may also reduce other physical properties that could be achieved by polyurethane or improve the properties of the materials during the use of polyurethane materials. Problems such as elution to the outside may occur. However, in the present application, said low adhesion can be achieved on polyurethane materials while not using or minimizing the amount of adhesion-reducing components such as plasticizers. Therefore, the present application can provide a material that has the advantages of polyurethane materials while solving the problem of high adhesive strength that is not required depending on the application.

The resin composition or its cured product can exhibit controlled adhesive strength to aluminum. For example, the upper limit of the adhesive force to aluminum is 1N/mm ² , 0.9N/mm ^{2 , 0.8N/mm 2} , 0.7N/mm ² , 0.6N/ ^{mm 2 ,} 0.5N/mm ² , 0.4N/mm ² , 0.3N/mm ² , 0.2N/mm ² , 0.1N/mm ² , 0.09N/mm ² , 0.08N/mm ² , 0.07N/mm ² , It may be 0.06 N/mm ² , 0.04 N/mm ² or 0.03 N/mm ² . The lower limit of the adhesive strength to aluminum is not particularly limited. In one example, the lower limit of the adhesive strength to aluminum is 0N/mm ² , 0.0001N/mm ² , 0.0005N/mm ² , 0.001N/mm ² , 0.005N/mm ² , 0.01N/mm ² , 0.015 N/mm ² , 0.02 N/mm ² , 0.025 N/mm ² or 0.03 N/mm ² . That is, the resin composition may be a resin composition whose adhesive strength to aluminum is substantially unmeasurable, or may be a resin composition which can form a cured product whose adhesive strength is substantially unmeasurable. The adhesive strength to aluminum is less than or equal to any one of the above upper limits, is greater than or equal to any one of the above lower limits, or is greater than or equal to any one of the above lower limits. It may be greater than or equal to any one lower limit, and may be less than or equal to any one of the above-mentioned upper limits. The adhesive strength to aluminum can be measured by the method described in the Examples of this specification.

The resin composition or its cured product can exhibit controlled adhesive strength to polyester. For example, the upper limit of the adhesive force to the polyester is 2,000gf/10mm, 1,800gf/10mm, 1,600gf/10mm, 1,400gf/10mm, 1,200gf/10mm, 1,000gf/10mm, 950gf/10mm , 900gf/10mm, 850gf/10mm, 800gf/10mm, 750gf/10mm, 700gf/10mm, 650gf/10mm, 600gf/10mm, 550gf/10mm, 500gf/10mm, 450gf/10mm, 400gf/10mm, 3 50gf/10mm, 300gf 20g f/10mm Or it may be 10gf/10mm. In the present application, the lower limit of the adhesive strength to the polyester is not particularly limited. In one example, the lower limit of the adhesive strength to the polyester may be 0 gf/10 mm. That is, the resin composition or its cured product does not need to exhibit substantially adhesive strength to polyester. Therefore, the adhesive force of the resin composition or its cured product to polyester may be 0 gf/10 mm or more. For example, the lower limit of the adhesive strength for the polyester is 0gf/10mm, 5gf/10mm, 10gf/10mm, 15gf/10mm, 20gf/10mm, 25gf/10mm, 30gf/10mm, 35gf/10mm, 40gf/10mm, 45gf /10mm, 50gf/10mm, 55gf/10mm, 65gf/10mm, 70gf/10mm, 75gf/10mm, 80gf/10mm, 85gf/10mm, 90gf/10mm or 95gf/10mm. The adhesive strength to the polyester is less than or equal to any one of the upper limits listed above, greater than or equal to any one of the lower limits listed above, or greater than or equal to any one of the lower limits listed above. It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits. The adhesive strength to the polyester can be measured by the method described in the Examples of this specification.

The resin composition or its cured product can exhibit the adhesive force to a specific adherend (for example, aluminum and/or polyester) and exhibit excellent thermal conductivity. For example, the lower limit of the thermal conductivity of the resin composition or its cured product is 1.2 W/mK, 1.4 W/mK, 1.6 W/mK, 1.8 W/mK, 2.0 W/mK, 2. It may be about 2W/mK, 2.4W/mK, 2.6W/mK or 2.8W/mK. There is no particular limit to the upper limit of the thermal conductivity. For example, the upper limit of the thermal conductivity of the resin composition or its cured product is about 10 W/mK, 9 W/mK, 8 W/mK, 7 W/mK, 6 W/mK, 5 W/mK, 4 W/mK, or 3 W/mK. It may be. The thermal conductivity is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits. The thermal conductivity of such a resin composition or its cured product can be measured by the method disclosed in the Examples described below.

The resin composition or its cured product can exhibit appropriate hardness. For example, if the hardness of the resin composition or its cured product is too high, it may become extremely brittle, which may cause problems. In addition, by adjusting the hardness of the resin composition or its cured product, it is possible to ensure impact resistance and vibration resistance, and ensure product durability, depending on the application.

For example, the upper limit of the shore OO type hardness of the resin composition or its cured product is 150, 140, 130, 120, 110, 100, 95, 90, 80, 70, 60, 50, or 45. The lower limit may be about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85. The shore OO type hardness is less than or equal to any one of the upper limits set forth above, greater than or equal to any one of the lower limits set forth above, or greater than or equal to any one of the lower limits set forth above; It may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits. The hardness of such a resin composition or its cured product can be measured by the method disclosed in the Examples below.

The resin composition or its cured product can also exhibit appropriate flexibility. For example, by adjusting the flexibility of the resin composition or its cured product to a desired level, the range of applications can be greatly expanded. For example, the lower limit of the radius of curvature of the resin composition or its cured product may be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and the upper limit is: It may be about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5 or 4. The radius of curvature is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. It may be greater than or equal to any one lower limit, and may be less than or equal to any one of the above-mentioned upper limits. The radius of curvature of such a resin composition or its cured product can be measured by the method disclosed in the Examples described below. Further, unless otherwise specified, the unit of radius of curvature in this specification is mm.

The resin composition of the present application may be insulating. That is, the resin composition has insulating properties and/or can form a cured body having insulating properties. For example, the resin composition or its cured product has a dielectric breakdown voltage of about 3 kV/mm or more, about 5 kV/mm or more, about 7 kV/mm or more, 10 kV/mm or more, 15 kV/mm or more, as measured in accordance with ASTM D149. Alternatively, it may be 20 kV/mm or more. The higher the value of the dielectric breakdown voltage, the better the insulation properties, and the upper limit is not particularly limited, but considering the composition of the resin composition, etc., the dielectric breakdown voltage may be approximately 50 kV/mm or less, 45 kV/mm or less, 40 kV/mm or less, 35 kV/mm or less, or 30 kV/mm or less. The dielectric breakdown voltage as described above can be controlled by adjusting the insulating properties of the resin composition, and can be achieved, for example, by applying an insulating filler within the resin layer. Generally, among fillers, ceramic fillers are known to be components that can ensure insulation.

The resin composition or its cured product may have flame retardancy. For example, the resin composition or its cured product can exhibit a V-0 rating in the UL 94 V Test (Vertical Burning Test). This makes it possible to ensure stability against fire and other accidents, which are a concern depending on the application of the resin composition.

The resin composition or its cured product may have a specific gravity of 5 or less. The specific gravity may be 4.5 or less, 4 or less, 3.5 or less, or 3 or less in other examples. A resin layer having a specific gravity within such a range is advantageous in providing a lighter product. The lower limit of the specific gravity is not particularly limited. For example, the specific gravity may be about 1.5 or more, or about 2 or more. In order for the resin composition or its cured product to exhibit the above specific gravity, the components added to the resin layer can be adjusted. For example, when adding a filler, use a filler that can ensure the desired properties (for example, thermal conductivity) even with the lowest possible specific gravity, that is, a filler that itself has a low specific gravity, or a filler that has been surface-treated. methods can be used.

The resin composition may have low shrinkage during or after curing. Through this, peeling and generation of voids that may occur during the application process can be prevented. The shrinkage rate can be appropriately adjusted within a range that can exhibit the above-mentioned effects, and may be, for example, less than 5%, less than 3%, or less than about 1%. The lower the shrinkage rate, the more advantageous it is, so the lower limit is not particularly limited.

The resin composition or its cured product may have a low coefficient of thermal expansion (CTE). Through this, peeling and generation of voids that may occur during application and use can be prevented. The thermal expansion coefficient can be appropriately adjusted within a range that can exhibit the above-mentioned effect, for example, less than 300 ppm/K, less than 250 ppm/K, less than 200 ppm/K, less than 150 ppm/K, or about 100 ppm/K. It may be less than The lower the coefficient of thermal expansion is, the more advantageous it is, so the lower limit thereof is not particularly limited.

The resin composition or its cured product may also have a 5% weight loss temperature of 400°C or higher in thermogravimetric analysis (TGA), and a residual amount of 70% by weight or higher at 800°C. It's okay. Such properties can further improve high temperature stability. In other examples, the 800°C residual amount may be about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, or about 90% by weight or more. In another example, the 800°C residual amount may be about 99% by weight or less. The thermogravimetric analysis (TGA) can be measured within the range of 25° C. to 800° C. at a heating rate of 20° C./min under a nitrogen (N2) atmosphere of 60 cm ³ /min. The thermogravimetric analysis (TGA) results can also be achieved through adjusting the composition of the resin composition. For example, the residual amount at 800° C. usually depends on the type and proportion of filler contained in the resin composition, and if an excessive amount of filler is included, the residual amount increases.

The resin composition of the present application may include a hydroxyl-functionalized component. The term hydroxy-active component may refer to compounds having all hydroxy groups present in the resin composition. Therefore, when one type of compound having a hydroxy group is present in the resin composition, this compound becomes the hydroxy group-functional component, and when two or more types of compounds having a hydroxy group are present in the resin composition, the compound becomes the hydroxy group-functional component. A mixture of two or more types of compounds serves as the hydroxy group-functional component.

Examples of the compound having a hydroxyl group that forms the hydroxy-functional component include oil-modified polyol compounds, general polyol compounds, and oil-modified alcohol compounds, but are not limited thereto.
The hydroxy functional component may include a polyol component. The polyol component may refer to all polyol compounds present within the resin composition. Therefore, when the resin composition has only one type of polyol compound, the one type of polyol compound becomes the polyol component, and when the resin composition contains two or more types of polyol compounds, the mixture of the two or more types of polyol compounds becomes the polyol component. It can be.

The term polyol compound as used herein means a compound containing two or more hydroxy groups. Such polyol compounds are also called polyfunctional polyol compounds. Such polyol compounds may be monomolecular, oligomeric or polymeric compounds. The number of hydroxy groups contained in the polyol compound is not particularly limited, but in one example, the lower limit of the number of hydroxy groups per molecule of the polyol compound may be 2 or 3, and the upper limit is: The number may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of hydroxy groups in the polyol compound is less than or equal to any one of the above upper limits, is greater than or equal to any one of the above lower limits, or is greater than or equal to any one of the above lower limits; It may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The number of hydroxy groups contained in a polyol compound can usually be confirmed by ¹ H NMR, and the number of hydroxy groups can be confirmed based on the peak present in the 3 ppm to 4 ppm region in ¹ H NMR.

The polyol compound may be an oil-modified polyol compound. The term oil-modified polyol compound means a compound containing two or more hydroxy groups and at the same time containing at least one terminal oil group. The oil group may be a straight chain or branched hydrocarbon group having 3 or more carbon atoms. Whether or not a polyol compound contains the hydrocarbon group can usually be confirmed by ¹ H NMR, but the presence of the hydrocarbon group can be determined based on the peak present in the 4 ppm to 5 ppm region in ¹ H NMR. The presence and number can be confirmed. Such polyol compounds may be monomolecular, oligomeric or polymeric compounds. By applying such an oil-modified polyol compound, it is possible to form a polyurethane material and achieve low adhesion to specific materials without using or minimizing the amount of adhesion-reducing components such as plasticizers. power can be secured.

The lower limit of the number of carbon atoms in the linear or branched hydrocarbon group that is the oil group is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 13, 14, 15, 16 or 17, and the upper limit is 50, 49, 48, 47, 46, 45, 44, 43, 42 pieces, 41 pieces, 40 pieces, 39 pieces, 38 pieces, 37 pieces, 36 pieces, 35 pieces, 34 pieces, 33 pieces, 32 pieces, 31 pieces, 30 pieces, 29 pieces, 28 pieces, 27 pieces, 26 pieces , 25 pieces, 24 pieces, 23 pieces, 22 pieces, 21 pieces, 20 pieces, 19 pieces, 18 pieces, 17 pieces, 16 pieces, 15 pieces, 14 pieces, 13 pieces, 12 pieces, 11 pieces or about 10 pieces. There may be. The number of carbon atoms is less than or equal to any one of the upper limits set forth above, greater than or equal to any one of the lower limits set forth above, or greater than or equal to any one of the lower limits set forth above; It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.

The straight or branched hydrocarbon group may or may not contain a double bond. When a double bond is included, the double bond may be a conjugated double bond or a cis double bond.

Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. In one example, the hydrocarbon group may be linked to the polyol compound via a carbonyl group or a carbonyloxy group, and in this case, the hydrocarbon group is an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, an alkyl It may be a carbonyloxy group, an alkenylcarbonyloxy group or an alkynylcarbonyloxy group. In the above, the lower limit of the number of carbon atoms in the alkyl group, alkenyl group, or alkynyl group is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13. , 14, 15, 16 or 17, and the upper limit is 50, 49, 48, 47, 46, 45, 44, 43, 42, 41 pieces, 40 pieces, 39 pieces, 38 pieces, 37 pieces, 36 pieces, 35 pieces, 34 pieces, 33 pieces, 32 pieces, 31 pieces, 30 pieces, 29 pieces, 28 pieces, 27 pieces, 26 pieces, 25 pieces , 24 pieces, 23 pieces, 22 pieces, 21 pieces, 20 pieces, 19 pieces, 18 pieces, 17 pieces, 16 pieces, 15 pieces, 14 pieces, 13 pieces, 12 pieces, 11 pieces or even about 10 pieces. good. The number of carbon atoms is less than or equal to any one of the upper limits set forth above, greater than or equal to any one of the lower limits set forth above, or greater than or equal to any one of the lower limits set forth above; It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.

The alkyl, alkenyl or alkynyl group may be linear or branched and optionally substituted with one or more substituents. When a substituent exists, there is no particular restriction on the type of the substituent, and for example, a halogen atom such as fluorine can be exemplified as the substituent.
In one example, the hydrocarbon group may be included in a substituent of Chemical Formula 1 below.

In Chemical Formula 1, R is the hydrocarbon group having 3 or more carbon atoms and being linear or branched. In Chemical Formula 1, the symbol * means that the moiety is linked to the polyol compound. Therefore, an oxygen atom in the substituent of Formula 1 may be connected to the polyol compound.
The specific type of the hydrocarbon group represented by R in Chemical Formula 1 is as described above. Therefore, the contents regarding the number of carbon atoms, types, forms, substituents, etc. of the hydrocarbon group described above may be applied in the same manner as above.

The number of hydrocarbon groups included in the polyol compound is not particularly limited. In one example, the lower limit of the number of hydrocarbon groups contained in the oil-modified polyol compound may be 1 or 2 per molecule, and the upper limit is 10, 9, or 8 per molecule. , 7 pieces, 6 pieces, 5 pieces, 4 pieces, 3 pieces, or about 2 pieces. The number of hydrocarbon groups is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or greater than or equal to any one of the above lower limits. It may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.
The polyol compound may have various forms as long as it contains the hydroxy group and hydrocarbon group.

In one example, the polyol compound may be a hydrocarbon compound such as an alkane, an alkene, or an alkyne, in which at least some of the hydrogen atoms are substituted with the hydroxy group and/or the hydrocarbon group. The number of carbon atoms in the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, from 1 to 20, from 1 to 16, from 1 to 8 or from 4 to 6.

Hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and/or hydrocarbon group may be substituted with the same carbon atom in the alkane, alkene, or alkyne, or may be substituted with another carbon atom.

In another example, the polyol compound may be a compound having a polyester skeleton or a polyether skeleton. In such a case, the polyol compound may be an oligomeric compound or a polymeric compound.
In one example, the polyol compound having a polyester skeleton is a so-called polyester polyol, and may be a polyol having a structure in which the hydrocarbon group is connected to such a polyester polyol.

The polyol compound having a polyether skeleton is a so-called polyether polyol, and may be a polyol having a structure in which the hydrocarbon group is connected to such a polyether polyol.
In one example, the polyester skeleton may be a so-called polycaprolactone skeleton, and the polyether skeleton may be a so-called polyalkylene skeleton.
In one example, the polyester skeleton may have a repeating unit represented by Formula 2 below.

In Chemical Formula 2, X ₁ and X ₂ are each independently a single bond or an oxygen atom, L ₁ may be an alkylene group, and n is an arbitrary number.

As used herein, the term "single bond" means that no atom exists at the site.
In chemical formula 2, the alkylene group may be an alkylene group having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, as an example. may be linear or branched.
As used herein, the term alkylene group refers to a divalent substituent formed by the removal of two hydrogen atoms from an alkane, where the two hydrogen atoms are separated from other carbon atoms of the alkane. One carbon atom of each can be eliminated, and an alkane can also be eliminated from one carbon atom.

As described later, in one example, the polyester skeleton may be a polycaprolactone skeleton, and in this case, L ₁ in the chemical formula 2 may be a linear alkylene group having 5 carbon atoms.

In Chemical Formula 2, n is an arbitrary number indicating the number of repeating units, and may be a number within the range of 1 to 25, for example.
The lower limit of n in chemical formula 2 may be about 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21 or 23, and the upper limit is 25, 23, 21, 19, 17 , 15, 13, 11, 9, 7, 5, or about 3. The n is less than or equal to any one of the above upper limits, is greater than or equal to any one of the above lower limits, or is any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

The skeleton of Chemical Formula 2 is a skeleton of a polyester polyol, and may be a skeleton of a so-called carboxylic acid polyol or a skeleton of a caprolactone polyol. Such a skeleton can be formed by a known method, for example, the skeleton of the carboxylic acid polyol can be formed by reacting a component containing a carboxylic acid and a polyol (ex. diol or triol), The skeleton of caprolactone polyol can be formed by reacting a component containing caprolactone and a polyol (ex. diol or triol). The carboxylic acid may be a dicarboxylic acid.

In the polyol compound having the skeleton of Chemical Formula 2, the hydroxyl group or the hydrocarbon group described above may be present at the end of the skeleton of Chemical Formula 2.
In such a case, the skeleton of Chemical Formula 2 may be represented by Chemical Formula 3 below.

In Chemical Formula 3, X ₁ , X ₂ , L ₁ and n are as defined in Chemical Formula 2, and R ₁ may be a hydroxy group or a substituent of Chemical Formula 4 below.

In Chemical Formula 4, X ₃ is a single bond or an oxygen atom, and R is the same as R in Chemical Formula 1 above.
In Chemical Formula 3, when R ₁ is a hydroxy group, X ₁ is a single bond, and when R ₁ is a substituent of Chemical Formula 4, any one of X ₁ and X ₃ is , is a single bond, and the other one is an oxygen atom.

The lower limit of the number of skeletons of the chemical formula 2 or 3 contained in the polyol compound may be about 1 or 2, and the upper limit is 10, 9, 8, 7, 6, 5. The number may be about 1, 4, 3, or 2. The number of skeletons is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.
The polyol compound having a polyester skeleton may have a linear or branched structure.

In the above, the linear structure is a structure in which a main chain containing the skeleton of the chemical formula 2 or 3 is present and no other polymer chain is connected to the main chain, and the branched structure is a structure in which the main chain includes the skeleton of the chemical formula 2 or 3. Alternatively, a chain containing the skeleton of Chemical Formula 2 or 3 may be bonded to the main chain containing the skeleton of Chemical Formula 2 or 3 as a side chain. In the above, the number of chains containing the skeleton of the chemical formula 2 or 3 that are connected as side chains in the branched structure is, for example, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. Or it may be one piece.

In one example, the polyol compound having a polyester skeleton is a compound in which at least a portion of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne are substituted with the hydroxy group and/or the skeleton of Chemical Formula 3. There may be. The number of carbon atoms in the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, from 1 to 20, from 1 to 16, from 1 to 8 or from 4 to 6.

Hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and/or the skeleton of Chemical Formula 3 may be substituted with the same carbon atom in the alkane, alkene, or alkyne, or may be substituted with another carbon atom.

In one example, the polyether skeleton may have a repeating unit represented by the following Chemical Formula 5.

In Chemical Formula 5, X ₄ and X ₅ are each independently a single bond or an oxygen atom, L ₂ may be an alkylene group, and m is an arbitrary number.
In the chemical formula 5, the alkylene group may be, for example, an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, It may be linear or branched.
In the chemical formula 5, m is an arbitrary number indicating the number of repeating units, and may be a number within the range of 1 to 25, for example.

The lower limit of m in Chemical Formula 5 may be about 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21 or 23, and the upper limit is 25, 23, 21, 19, 17 , 15, 13, 11, 9, 7, 5 or 3. The m is less than or equal to any one of the above upper limits, is greater than or equal to any one of the above lower limits, or is any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

In the polyol compound having the skeleton of Chemical Formula 5, the hydroxy group or the above-mentioned hydrocarbon group may be present at the end of the skeleton of Chemical Formula 5.
In such a case, the skeleton of Chemical Formula 5 may be represented by Chemical Formula 6 below.

In Chemical Formula 6, X ₄ , X ₅ , L ₂ and m are as defined in Chemical Formula 5, and R ₂ may be a hydroxy group or a substituent of Chemical Formula 7 below.

In Chemical Formula 7, X ₆ is a single bond or an oxygen atom, and R is the same as R in Chemical Formula 1 above.
In Chemical Formula 6, when R ₂ is a hydroxy group, X ₄ is a single bond, and when R ₂ is a substituent of Chemical Formula 7, any one of X ₄ and X ₆ is , is a single bond, and the other one is an oxygen atom.

The lower limit of the number of skeletons of the chemical formula 5 or 6 contained in the polyol compound may be about 1 or 2, and the upper limit is 10, 9, 8, 7, 6, 5. The number may be about 1, 4, 3, or 2. The number of skeletons is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The polyol compound having a polyether skeleton may have a linear or branched structure.

In the above, the linear structure is a structure in which a main chain containing the skeleton of the chemical formula 5 or 6 is present, and no other polymer chain is connected to the main chain, and the branched structure is a structure that has a main chain containing the skeleton of the chemical formula 5 or 6. Alternatively, a chain containing the skeleton of Chemical Formula 5 or 6 may be bonded to the main chain containing the skeleton of Chemical Formula 5 or 6 as a side chain. In the above, the number of chains containing the skeleton of the chemical formula 5 or 6 that are connected as side chains in the branched structure is, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2. Or it may be one piece.

In one example, the polyol compound having a polyether skeleton is a compound in which at least a portion of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne are substituted with a hydroxy group and/or a skeleton represented by the chemical formula 5. There may be. The number of carbon atoms in the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, from 1 to 20, from 1 to 16, from 1 to 8 or from 4 to 6.

Hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and/or the skeleton of Chemical Formula 5 may be substituted with the same carbon atom in the alkane, alkene, or alkyne, or may be substituted with another carbon atom.

When the polyol compound described above is an oligomeric or polymeric compound, the compound may have an appropriate level of molecular weight.

For example, the lower limit of the weight average molecular weight of the oligomeric or polymeric polyol compound is 100 g/mol, 200 g/mol, 300 g/mol, 400 g/mol, 500 g/mol, 600 g/mol, 700 g/mol, 800 g /mol or about 900g/mol, and the upper limit thereof is 5000g/mol, 4500g/mol, 4000g/mol, 3500g/mol, 3000g/mol, 2500g/mol, 2000g/mol, 1500g/mol, 1000g /mol or about 800g/mol. The weight average molecular weight is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

By applying the oil-modified polyol compound as described above, the desired physical properties can be more effectively ensured.

The oil-modified polyol compound may be present in an appropriate proportion within the resin composition. For example, the lower limit of the content of the oil-modified polyol compound in the resin composition is 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight. , 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight or about 95% by weight. , the upper limits are 100% by weight, 95% by weight, 90% by weight, 85% by weight, 80% by weight, 75% by weight, 70% by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight. It may be about % by weight, 40% by weight, 35% by weight, 30% by weight, 25% by weight or 20% by weight. Said content is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. It may be greater than or equal to any one lower limit, and may be less than or equal to any one of the above-mentioned upper limits.

The content of the oil-modified polyol compound is the content in the one-component resin composition when the resin composition is one-component, and the content of the oil-modified polyol compound in the one-component resin composition when the resin composition is one-component. This is the content in the part where the modified polyol compound is present. For example, when a two-component resin composition includes a physically separated base part and a curing agent part, and the oil-modified polyol compound is contained in the base part, the content of the oil-modified polyol in the base part is The content may be based on the total weight. Moreover, when the resin composition contains a solvent and/or a filler, the content is based on the weight excluding the content of the solvent and filler.

In another example, the content of the oil-modified polyol compound may be based on 100% by weight of all polyol components present in the resin composition.

In other examples, when the resin composition includes a filler component described below, the lower limit of the content of the oil-modified polyol compound based on 100 parts by weight of the filler component is 1 part by weight, 3 parts by weight, 5 parts by weight, and 7 parts by weight. part, 9 parts by weight, 11 parts by weight, or 13 parts by weight, and the upper limit thereof is 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight. part, 8 parts, 6 parts, 4 parts, or 3 parts by weight. Said content is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. It may be greater than or equal to any one lower limit, and may be less than or equal to any one of the above-mentioned upper limits.

The ratio to the filler component is the ratio to 100 parts by weight of the total filler component contained in the resin composition when the resin composition is a one-component type, and the ratio to the oil-modified polyol when the resin composition is a two-component type. This is the ratio to 100 parts by weight of the total filler component present in the part (base part or curing agent part) containing the filler.

The hydroxy-active component may also contain an alcohol compound as a further component, if necessary. The term alcohol compound means a compound containing one hydroxy group per molecule. Such alcohol compounds may be monomolecular, oligomeric or polymeric compounds.

Moreover, an oil-modified alcohol compound can be used as the alcohol compound. The term oil-modified alcohol compound means a compound containing one hydroxyl group per molecule and at the same time containing at least one terminal end of said oil group, i.e. a linear or branched hydrocarbon group having 3 or more carbon atoms. do. The method for confirming the number of hydroxy groups, the number of hydrocarbon groups, etc. in the above is the same as in the case of the polyol compound. Such alcohol compounds may be monomolecular, oligomeric or polymeric compounds. By applying such an oil-modified alcohol compound together with the above-mentioned oil-modified polyol compound, it is possible to form a polyurethane material, and it is possible to achieve specific Low adhesion strength can be ensured for materials such as

The oil-modified alcohol compound may have a similar form to the oil-modified polyol compound except that it contains one hydroxy group per molecule. Therefore, the content explained regarding the oil-modified polyol compound can be equally applied to the oil-modified alcohol compound.

That is, for example, the lower limit of the number of carbon atoms in the linear or branched hydrocarbon group present in the oil-modified alcohol compound is 4, 5, 6, 7, 8, 9, 10. , 11, 12, 13, 14, 15, 16 or 17, and the upper limit is 50, 49, 48, 47, 46, 45, 44 pieces, 43 pieces, 42 pieces, 41 pieces, 40 pieces, 39 pieces, 38 pieces, 37 pieces, 36 pieces, 35 pieces, 34 pieces, 33 pieces, 32 pieces, 31 pieces, 30 pieces, 29 pieces, 28 pieces , 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11 or about 10 pieces. The number of carbon atoms is less than or equal to any one of the upper limits set forth above, greater than or equal to any one of the lower limits set forth above, or greater than or equal to any one of the lower limits set forth above; It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.

The straight or branched hydrocarbon group may or may not contain a double bond. When a double bond is included, this double bond may be a conjugated double bond or a cis double bond.

Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. In one example, the hydrocarbon group may be linked to the alcohol compound via a carbonyl group or a carbonyloxy group, and in this case, the hydrocarbon group is an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, an alkyl It may be a carbonyloxy group, an alkenylcarbonyloxy group or an alkynylcarbonyloxy group.

The lower limit of the number of carbon atoms in the alkyl group, alkenyl group or alkynyl group is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, The number may be about 14, 15, 16 or 17, and the upper limit is 50, 49, 48, 47, 46, 45, 44, 43, 42, 41 pieces, 40 pieces, 39 pieces, 38 pieces, 37 pieces, 36 pieces, 35 pieces, 34 pieces, 33 pieces, 32 pieces, 31 pieces, 30 pieces, 29 pieces, 28 pieces, 27 pieces, 26 pieces, 25 pieces, It may be about 24 pieces, 23 pieces, 22 pieces, 21 pieces, 20 pieces, 19 pieces, 18 pieces, 17 pieces, 16 pieces, 15 pieces, 14 pieces, 13 pieces, 12 pieces, 11 pieces, or about 10 pieces. . The number of carbon atoms is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or less than or equal to any one of the above lower limits; It may be within a range that is greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.

The alkyl, alkenyl or alkynyl group may be linear or branched and optionally substituted with one or more substituents. When a substituent exists, there is no particular restriction on the type of the substituent, and for example, a halogen atom such as fluorine can be exemplified as the substituent.

In one example, the hydrocarbon group of the oil-modified alcohol compound may also be included in the substituents of Formula 1 above. At this time, the details regarding the substituents of Chemical Formula 1 are also the same as in the case of the oil-modified polyol compound.
The number of hydrocarbon groups contained in the alcohol compound is not particularly limited, but in one example, the lower limit of the number of hydrocarbon groups contained in the alcohol compound may be about 1 or 2 per molecule. The upper limit may be approximately 10, 9, 8, 7, 6, 5, 4, 3, or 2 per molecule. The number of carbon atoms is less than or equal to any one of the upper limits set forth above, greater than or equal to any one of the lower limits set forth above, or greater than or equal to any one of the lower limits set forth above; It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.
The alcohol compound may have various forms as long as it contains the hydroxy group and hydrocarbon group.

In one example, the alcohol compound may be a hydrocarbon compound such as an alkane, an alkene, or an alkyne, in which at least some of the hydrogen atoms are substituted with one hydroxy group and/or the hydrocarbon group. . The number of carbon atoms in the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, from 1 to 20, from 1 to 16, from 1 to 8 or from 4 to 6.
Hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and/or hydrocarbon group may be substituted with the same carbon atom in the alkane, alkene, or alkyne, or may be substituted with another carbon atom.

In another example, the alcohol compound may be a compound having a polyester skeleton or a polyether skeleton. In such a case, the alcohol compound may be an oligomeric compound or a polymeric compound.

As in the case of polyol compounds, the polyester skeleton may be a so-called polycaprolactone skeleton, and the polyether skeleton may be a so-called polyalkylene skeleton.
In one example, the polyester skeleton may have a repeating unit represented by Formula 2. At this time, the specific details regarding the repeating unit of Chemical Formula 2 are the same as those for the polyol compound.

Therefore, even in the case of oil-modified alcohol compounds, the hydroxyl group or the above-mentioned hydrocarbon group may be present at the end of the skeleton of Chemical Formula 2 in the alcohol compound having the skeleton of Chemical Formula 2, and in such a case, , the skeleton of Chemical Formula 2 may be represented by Chemical Formula 3. At this time, the specific content regarding the skeleton of Chemical Formula 3 is the same as in the case of the polyol compound.

The lower limit of the number of skeletons of the chemical formula 2 or 3 of the alcohol compound may be about 1 or 2 on the premise that the compound contains one hydroxy group per molecule, and the upper limit is 10. , 9, 8, 7, 6, 5, 4, 3, or 2. The number of skeletons is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The alcohol compound having a polyester skeleton may also have a linear or branched structure.
In the above, the linear structure is a structure in which a main chain containing the skeleton of the chemical formula 2 or 3 is present and no other polymer chain is connected to the main chain, and the branched structure is a structure in which the main chain includes the skeleton of the chemical formula 2 or 3. Alternatively, a chain containing the skeleton of Chemical Formula 2 or 3 may be bonded to the main chain containing the skeleton of Chemical Formula 2 or 3 as a side chain. In the above, the number of chains containing the skeleton of the chemical formula 2 or 3 that are connected as side chains in the branched structure is, for example, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. Or it may be one piece.

In one example, the alcohol compound having a polyester skeleton is also a compound in which at least a portion of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne are substituted with the hydroxy group and/or the skeleton of Chemical Formula 3. There may be. The number of carbon atoms in the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, from 1 to 20, from 1 to 16, from 1 to 8 or from 4 to 6.

Hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and/or the skeleton of Chemical Formula 3 may be substituted with the same carbon atom in the alkane, alkene, or alkyne, or may be substituted with another carbon atom.

The polyether skeleton of the alcohol compound may also be a skeleton having a repeating unit represented by Formula 5, in one example. At this time, the specific content regarding Chemical Formula 5 is the same as in the case of the polyol compound.
Further, in the alcohol compound having the skeleton of Chemical Formula 5, the hydroxy group or the above-mentioned hydrocarbon group may be present at the end of the skeleton of Chemical Formula 5, which may be the skeleton of Chemical Formula 6. At this time, the specific content regarding Chemical Formula 6 is the same as in the case of the polyol compound.
On the premise that the alcohol compound has one hydroxy group per molecule, the lower limit of the number of skeletons of the chemical formula 5 or 6 contained in the alcohol compound may be about 1 or 2; may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of skeletons is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The alcohol compound having a polyether skeleton may have a linear or branched structure.
In the above, the linear structure is a structure in which a main chain containing the skeleton of the chemical formula 5 or 6 is present, and no other polymer chain is connected to the main chain, and the branched structure is a structure that has a main chain containing the skeleton of the chemical formula 5 or 6. Alternatively, a chain containing the skeleton of Chemical Formula 5 or 6 may be bonded to the main chain containing the skeleton of Chemical Formula 5 or 6 as a side chain. In the above, the number of chains containing the skeleton of the chemical formula 5 or 6 that are connected as side chains in the branched structure is, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2. Or it may be one piece.

In one example, the alcohol compound having a polyether skeleton is a compound in which at least a portion of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne are substituted with a hydroxy group and/or a skeleton of the chemical formula 5. There may be. The number of carbon atoms in the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, from 1 to 20, from 1 to 16, from 1 to 8 or from 4 to 6.
Hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and/or the skeleton of Chemical Formula 5 may be substituted with the same carbon atom in the alkane, alkene, or alkyne, or may be substituted with another carbon atom.

When the alcohol compound mentioned above is an oligomeric or polymeric compound, the compound may have an appropriate level of molecular weight.

For example, the lower limit of the weight average molecular weight of the oligomeric or polymeric alcohol compound is 10 g/mol, 200 g/mol, 300 g/mol, 400 g/mol, 500 g/mol, 600 g/mol, 700 g/mol, 800 g/mol, It may be about mol, 900g/mol, 1000g/mol, 1200g/mol, 1400g/mol, 1600g/mol or 1800g/mol, and the upper limit thereof is 5000g/mol, 4500g/mol, 4000g/mol, 3500g/mol. It may be about mol, 3000g/mol, 2500g/mol, 2000g/mol, 1500g/mol, 1000g/mol or 800g/mol. The weight average molecular weight is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

By applying the oil-modified alcohol compound as described above, the desired physical properties can be more effectively ensured.

The lower limit of the content of the oil-modified alcohol compound relative to 100 parts by weight of the oil-modified polyol compound is 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight. Parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, 200 parts by weight , 210 parts by weight, 220 parts by weight, 230 parts by weight, 240 parts by weight, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, 290 parts by weight or about 300 parts by weight, and the upper limit thereof is , 1,000 parts by weight, 950 parts by weight, 900 parts by weight, 850 parts by weight, 800 parts by weight, 750 parts by weight, 700 parts by weight, 650 parts by weight, 600 parts by weight, 550 parts by weight, 500 parts by weight, 450 parts by weight , 400 parts by weight, 350 parts by weight, 300 parts by weight, 250 parts by weight, 200 parts by weight, 150 parts by weight, 100 parts by weight, 90 parts by weight, 80 parts by weight, 70 parts by weight or about 60 parts by weight. . Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

The proportion of the oil-modified polyol compound can be changed in consideration of the overall composition and desired physical properties of the resin composition.

Among the polyol components of the hydroxy-functional component, a component containing only the oil-modified polyol compound and the oil-modified alcohol compound may be referred to as an oil-modified component. In this case, the lower limit of the weight average molecular weight of the entire oil-modifying component is 10 g/mol, 200 g/mol, 300 g/mol, 400 g/mol, 500 g/mol, 600 g/mol, 700 g/mol, 800 g/mol, It may be about 900g/mol, 1000g/mol, 1200g/mol, 1400g/mol, 1600g/mol or 1800g/mol, and the upper limit is 5,000g/mol, 4500g/mol, 4000g/mol, 3500g/mol. It may be about mol, 3000g/mol, 2500g/mol, 2000g/mol, 1500g/mol, 1000g/mol or 800g/mol. The weight average molecular weight is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The oil-modified polyol compound or alcohol compound can be synthesized by a known synthesis method. That is, the compound can be produced by reacting a compound capable of introducing the hydrocarbon group corresponding to the oil-modified moiety with a known polyol compound. At this time, examples of compounds into which the hydrocarbon group can be introduced include saturated or unsaturated fatty acids, and specific examples include butyric acid, caproic acid, and 2-ethylhexanoic acid. hexanoic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid c acid), stearic acid Examples include, but are not limited to, linoleic acid, linoleic acid, and oleic acid. By adjusting the reaction ratio of the fatty acid and the polyol compound in the above process, it is also possible to produce a mixture (oil-modified component) containing the polyol compound and the alcohol compound, depending on the case.

Further, there is no particular restriction on the type of polyol compound that reacts with the saturated or unsaturated fatty acid. For example, an appropriate type of general polyol compounds described below can be used, but the invention is not limited thereto. .

The resin composition may further include a polyol compound different from the oil-modified polyol compound. In such a case, the polyol compound does not contain the aforementioned oil group, that is, a straight chain or branched hydrocarbon group having three or more carbon atoms. For convenience, such polyol compounds may be referred to herein as general polyol compounds.

The lower limit of the number of carbon atoms in the hydrocarbon group that does not contain a general polyol compound is 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 The number may be about 15, 16, or 17, and the upper limit is 50, 49, 48, 47, 46, 45, 44, 43, 42, 41. , 40 pieces, 39 pieces, 38 pieces, 37 pieces, 36 pieces, 35 pieces, 34 pieces, 33 pieces, 32 pieces, 31 pieces, 30 pieces, 29 pieces, 28 pieces, 27 pieces, 26 pieces, 25 pieces, 24 The number may be approximately 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10. The number of carbon atoms is less than or equal to any one of the upper limits set forth above, greater than or equal to any one of the lower limits set forth above, or greater than or equal to any one of the lower limits set forth above; It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits. In one example, the hydrocarbon group may be an alkyl, alkenyl or alkynyl group having the number of carbon atoms.

The general polyol compound may contain two or more hydroxy groups per molecule, and such a polyol compound may be a monomolecular, oligomeric, or polymeric compound. The number of hydroxy groups contained in the general polyol compound is not particularly limited, but in one example, the lower limit of the number of hydroxy groups contained in the general polyol compound may be about 2 or 3 per molecule; may be about 10, 9, 8, 7, 6, 5, 4, 3 or 2 per molecule. The number of hydroxy groups is less than or equal to any one of the upper limits listed above, is greater than or equal to any one of the lower limits listed above, or is greater than or equal to any one of the lower limits listed above. It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.
General polyol compounds may have various forms.

In one example, the general polyol compound may be a polyester polyol. As polyester polyols, for example, so-called carboxylic acid polyols or caprolactone polyols can be used.

In one example, the polyester polyol may have a skeleton having a repeating unit represented by Formula 8 below.

In Chemical Formula 8, X ₇ and X ₈ are each independently a single bond or an oxygen atom, L ₃ may be an alkylene group, and p is an arbitrary number.
In the chemical formula 8, the alkylene group may be an alkylene group having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, as an example. It may be linear or branched.

When the polyester polyol is a polycaprolactone polyol, _L3 in Formula 8 may be a linear alkylene group having 5 carbon atoms.
Further, in the chemical formula 8, p is an arbitrary number indicating the number of repeating units, and may be a number within the range of 1 to 25, for example.

The lower limit of p in the chemical formula 8 may be about 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21 or 23, and the upper limit is about 25, 23, 21, 19, It may be about 17, 15, 13, 11, 9, 7, 5 or 3. The p is less than or equal to any one of the above upper limits, is greater than or equal to any one of the above lower limits, or is any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

The polyester polyol having the skeleton of Chemical Formula 8 may be a so-called carboxylic acid polyol or caprolactone polyol. Such a polyol compound can be formed by a known method. For example, the carboxylic acid polyol can be formed by reacting a component containing a carboxylic acid and a polyol (ex. diol or triol), and caprolactone A polyol can be formed by reacting a component containing caprolactone and a polyol (ex. diol or triol). The carboxylic acid may be a dicarboxylic acid.

In the polyol compound having the skeleton of Chemical Formula 8, the hydroxyl group may be present at the end of the skeleton of Chemical Formula 8, or may be present at another site of the polyester polyol.
The lower limit of the number of skeletons represented by the chemical formula 8 contained in the general polyol compound may be 1 or 2, and the upper limit is 10, 9, 8, 7, 6, 5, 4. The number may be about 1, 3, 2, or 1. The number of skeletons is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The polyol compound having a polyester skeleton may have a linear or branched structure.
In the above, the linear structure is a structure in which a main chain including the skeleton of the chemical formula 8 is present and no other polymer chain is connected to the main chain, and the branched chain structure is a structure including the skeleton of the chemical formula 8. It may also be in the form that a chain containing the skeleton of the chemical formula 8 is bonded to the main chain as a side chain. In the above, the number of chains containing the skeleton of the chemical formula 8 connected as side chains in the branched structure is, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1. It may be one piece.

As another example, a polyol having an alkanediol unit, a polyol unit, and a dicarboxylic acid unit may be used as the general polyol compound. Such a polyol may be a mixture of the above-mentioned alkanediols, polyols and dicarboxylic acids, or may be a reaction product thereof. At this time, the alkanediol is 3-methyl-1,5-pentanediol, 1,9-nonanediol, or 1,6-hexane. Examples include diol compounds having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, or 4 to 12 carbon atoms, such as diol (1,6-hexanediol). Further, the polyol may include 3 to 10 polyols, 3 to 9 polyols, 3 to 8 polyols, 3 to 7 polyols, 3 to 6 polyols, 3 to 5 polyols, or 3 polyols such as trimethylolpropane. Examples include alkanes having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, or 4 to 12 carbon atoms substituted with 5 to 4 hydroxy groups. Examples of the dicarboxylic acid include adipic acid, terephthalic acid, isophthalic acid, and sebacic acid. Such types of polyol compounds include, for example, Kuraray's P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, Known product names such as F-2010, F-3010, P-2011, P-520, P-2020, P-1012, P-2012, P-630, P-2030, P-2050 or N-2010. ing.

As the general polyol, a polyol having a weight average molecular weight within the range of 100 g/mol to 5,000 g/mol can be used. Through the use of such polyols, the desired effects can be more effectively achieved.

When the general polyol compound is included, the lower limit of the weight ratio of the general polyol compound to 100 parts by weight of the oil-modified polyol compound is 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, and 10 parts by weight. , 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight It may be about 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight or 100 parts by weight, and the upper limit is 200 parts by weight, 190 parts by weight, 180 parts by weight, 170 parts by weight, 160 parts by weight. Parts by weight, 150 parts by weight, 140 parts by weight, 130 parts by weight, 120 parts by weight, 110 parts by weight, 100 parts by weight, 90 parts by weight, 80 parts by weight, 70 parts by weight, 60 parts by weight, 50 parts by weight, 40 parts by weight , 30 parts by weight, 20 parts by weight or about 10 parts by weight. Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

In another example, when the general polyol compound is included, the lower limit of the content of the general polyol compound is 1 part by weight and 5 parts by weight with respect to the total of 100 parts by weight of the oil-modified polyol and oil-modified alcohol. , 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or about 40 parts by weight, and the upper limit thereof is 200 parts by weight, 190 parts by weight, 180 parts by weight. , 170 parts by weight, 160 parts by weight, 150 parts by weight, 140 parts by weight, 130 parts by weight, 120 parts by weight, 110 parts by weight, 100 parts by weight, 90 parts by weight, 80 parts by weight, 70 parts by weight, 60 parts by weight, 50 parts by weight The amount may be about 40 parts by weight, 30 parts by weight, 20 parts by weight or 10 parts by weight. Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.
The above ratio can also be changed in consideration of the composition of the entire resin composition and the intended use.

The resin composition may contain, as a further component, a curing agent that reacts with the polyol compound and/or alcohol compound.

Various types of curing agents can be used, but when the resin composition is a polyurethane composition, polyisocyanate can be used as the curing agent. The term polyisocyanate means a compound having two or more isocyanate groups. The lower limit of the number of isocyanate groups that the polyisocyanate has may be about 2 or 3, and the upper limit is 10, 9, 8, 7, 6, 5, 4, 3. Or it may be about two pieces. The number of isocyanate groups is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or more than or equal to any one of the above lower limits. It may be greater than or equal to any one lower limit and less than or equal to any one of the above-mentioned upper limits.

The type of polyisocyanate used as a curing agent is not particularly limited, but a non-aromatic polyisocyanate containing no aromatic group can be used in order to ensure the desired physical properties.

Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, methyl norbornane diisocyanate, ethylene diisocyanate, propylene diisocyanate or tetramethylene diisocyanate; transcyclohexane-1,4-diisocyanate; Alicyclic polyisocyanates such as isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane diisocyanate or dicyclohexylmethane diisocyanate; or carbodiimide-modified polyisocyanates or isocyanurate-modified polyisocyanates of any one or more of the above can be used. Further, as the polyisocyanate, an addition reaction product of the above-mentioned diisocyanate and a polyol (eg, trimethylolpropane, etc.) may be used. Furthermore, a mixture of two or more of the compounds listed above can be used.

The application rate of the polyisocyanate can be adjusted in consideration of the number of hydroxyl groups present in the hydroxy functional component contained in the resin composition and the physical properties after curing.
For example, the polyisocyanate has an equivalent ratio (OH/NCO) of the number of hydroxy groups (OH) present in the hydroxy functional component present in the resin composition and the number (NCO) of isocyanate groups present in the polyisocyanate. may be contained in the resin composition so that the number is within the range of 50 to 1,000.

The method for calculating the equivalence ratio (OH/NCO) is known.
For example, if the resin composition is a two-component type, the hydroxyl-active component is contained in the base part, and the polyisocyanate is contained in the curing agent part, the equivalence ratio OH/NCO is calculated by the following general formula 1. be able to.

In the general formula 1, _D1 is the density of the base part, _D2 is the density of the curing agent part, and _W1 is the weight ratio of the polyol compound or alcohol compound present in the base part. OH% is the proportion of hydroxyl groups contained in the polyol compound or alcohol compound having the weight ratio of _W1 , _W2 is the weight proportion of the polyisocyanate present in the curing agent part, and NCO% is the proportion of isocyanate groups contained in the polyisocyanate having the weight ratio of _W2 , DN is 42 Da as the Dalton mass of the isocyanate group, and DO is 17 Da as the Dalton mass of the hydroxy group.

The above _W1 is the weight % (based on the total weight of the main part) of each polyol compound or alcohol compound present in the main part, and the OH% of the compound is the percentage by weight of each polyol compound or alcohol compound present in the main part. It is the percentage of hydroxyl groups contained, and is calculated by dividing the product of the number of moles of hydroxyl groups contained in a single polyol compound or alcohol compound and the molar mass of the hydroxyl group by the molar mass of the single polyol compound or alcohol compound, and then dividing 100 by the molar mass of the single polyol compound or alcohol compound. Find by multiplying.

In the above, W ₂ is the weight% of each polyisocyanate present in the curing agent part (based on the total weight of the curing agent part), and the NCO% of the compound is contained in 1 mole of each polyisocyanate compound. % of NCO groups, and is determined by dividing the product of the number of moles of NCO groups contained in a single polyisocyanate compound and the molar mass of the NCO group by the molar mass of the single polyisocyanate compound, and then multiplying by 100.
Furthermore, in the general formula 1, the Dalton mass is a constant.

The lower limit of the equivalent ratio (OH/NCO) is 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, It may be about 240, 250 or 260, and the upper limit thereof is 1000, 900, 800, 700, 600, 500, 400, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, It may be about 200, 190, 180, 170, 160, 150, 140, 130, 120, 110 or 100. The equivalence ratio is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. It may be greater than or equal to any one lower limit, and may be less than or equal to any one of the above-mentioned upper limits.

The resin composition may further include a filler component. The term filler component means a component consisting of filler, ie a component containing only filler.
In one example, the filler component may include two or more types of fillers that have different average particle sizes from each other. In one example, the filler component may include three or more types of fillers having different average particle diameters, three to six fillers, three to five fillers, three to four fillers, or three fillers having different average particle diameters. It may also consist of a seed filler. That is, in one example, the filler component may include 3 to 6 types, 3 to 5 types, 3 to 4 types, or only 3 types of fillers having different average particle diameters.

In another example, the filler component may exhibit at least two peaks in a volume curve of particle size distribution measured using laser diffraction. In one example, the filler component may exhibit 3 or more peaks, 3 to 6, 3 to 5, 3 to 4, or 3 peaks in the volume curve of the particle size distribution. can. For example, a range of filler components exhibiting three peaks does not include filler components exhibiting one, two, or four or more peaks.

The average particle diameter of the filler of the present application refers to the particle diameter at which the volume accumulation is 50% in the volume curve of the particle size distribution measured by laser diffraction, and is also referred to as the median diameter. That is, in this application, the particle size distribution is determined on a volume basis using the laser diffraction method, and the particle diameter at the point where the cumulative value is 50% on a cumulative curve with the total volume as 100% is defined as the average particle diameter. Such an average particle size is referred to as the median particle size or D50 particle size in other examples.

Therefore, the two types of fillers having different average particle diameters in the above may mean fillers having different particle diameters at the point where the cumulative value is 50% in the volume curve of the particle size distribution.
Usually, when two or more fillers having different average particle sizes are mixed to form a filler component, a volume curve of particle size distribution measured using a laser diffraction method for the filler component. In this case, peaks corresponding to the types of mixed fillers appear. Therefore, for example, when a filler component is formed by mixing three types of fillers with different average particle sizes, the volume curve of the particle size distribution measured using the laser diffraction method for the filler component is Indicates peak.

The filler component of the resin composition of the present application may be a thermally conductive filler component. The term "thermally conductive filler component" means a filler component that functions so that the resin composition or its cured product exhibits the above-mentioned thermal conductivity.

In one example, the filler component may include at least a first filler with an average particle size of 60 μm to 200 μm, a second filler with an average particle size of 10 μm to 30 μm, and a third filler with an average particle size of 5 μm or less. good.

The lower limit of the average particle size of the first filler may be about 62 μm, 62 μm, 64 μm, 66 μm, or about 68 μm, and the upper limit is 200 μm, 195 μm, 190 μm, 185 μm, 180 μm, 175 μm, 170 μm, 165 μm, 160 μm. , 155 μm, 150 μm, 145 μm, 140 μm, 135 μm, 130 μm, 125 μm, about 120 μm, 115 μm, 110 μm, 105 μm, 100 μm, 95 μm, 90 μm, 85 μm, 80 μm, or about 75 μm. The average particle diameter of the first filler is less than or equal to any one of the above upper limits, greater than or greater than any one of the above lower limits, or more than or equal to any one of the above lower limits. It may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The lower limit of the average particle size of the second filler may be about 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, and the upper limit is 29 μm, 28 μm, 27 μm, 26 μm, It may be about 25 μm, 24 μm, 23 μm, 22 μm, 21 μm or about 20 μm. The average particle size of the second filler is less than or equal to any one of the above upper limits, greater than or greater than any one of the above lower limits, or more than or equal to any one of the above lower limits. It may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

The lower limit of the third filler may be approximately 0.01 μm, 0.1 μm, approximately 0.5 μm, 1 μm, 1.5 μm, or 2 μm, and the upper limit thereof may be approximately 5 μm, 4.5 μm, approximately 4 μm, 3. It may be about 5 μm, 3 μm, 2.5 μm or 2 μm. The average particle size of the third filler is less than or equal to any one of the above upper limits, greater than or greater than any one of the above lower limits, or more than or equal to any one of the above lower limits. It may be greater than or equal to any one of the lower limits, and may be less than or equal to any one of the above-mentioned upper limits.

In the filler component, the ratio (D1/D3) of the average particle size (D1) of the first filler to the average particle size (D3) of the third filler may be in the range of 25 to 300.
In one example, when the filler component includes two or more types of fillers having different average particle diameters, the third filler may be the filler with the smallest average particle diameter among the fillers included in the filler component; When the filler component includes two or more types of fillers with different average particle diameters, the first filler may be the filler with the largest average particle diameter among the fillers included in the filler component. In such a state, the above particle size ratio can be satisfied.

The lower limit of the ratio (D1/D3) is 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 40, 50, 60, 70, 80, 90, 100, 110, 120. , 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230 or 235, and the upper limit thereof is 300, 290, 280, 270, 260, 250, 240, 220. , 200, 180, 160, 140, 120, 100, 95, 90, 85, 80, 75, 70, 65 or about 60. Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

In the filler component, the lower limit of the ratio (D1/D2) of the average particle size (D1) of the first filler to the average particle size (D2) of the second filler is 3, 3.1, 3.2, 3.3. , about 3.4 or 3.5, or about 20, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5 or 4. . Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

Examples of fillers include aluminum oxide (alumina: Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), beryllium oxide (BeO), Zinc oxide (ZnO), magnesium oxide (MgO), aluminum hydroxide (Al(OH) ₃ ), magnesium hydroxide (Mg(OH) ₂ ), calcium hydroxide, hydromagnesite, calcium carbonate (CaCO ₃ ) and/ Alternatively, a ceramic filler such as Boehmite can be used. Such a filler is advantageous in satisfying the thermal conductivity within the above-mentioned range, and furthermore, by applying the ceramic filler, it is possible to satisfy the above-mentioned insulation properties.

The upper limit of the proportion of the filler component in the resin composition is 99% by weight, 98% by weight, 97% by weight, 96% by weight, 95% by weight, 94.5% by weight, 94% by weight, 93.5% by weight. %, 93% by weight, 92.5% by weight, 92% by weight, 91.5% by weight, 91% by weight, 90.5% by weight, 90.0% by weight, 89.5% by weight, 89.0% by weight, It may be about 88.5% by weight or 88.0% by weight, and the lower limit thereof is about 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, about 75% by weight, 76% by weight. %, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt% or about 88 wt% It may be. Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

The content of the filler component is the proportion based on the total weight of the resin composition when the resin composition is a one-component resin composition, and the content of the filler component is the proportion based on the total weight of the resin composition when the resin composition is a two-component resin composition. The ratio may be based on the total weight of the base resin part and the curing agent part of the two-component resin composition, or the ratio may be based on the total weight of the base resin or the curing agent part alone.

When the resin composition is a two-component resin composition, the filler component to be applied to the final cured product is divided into substantially the same amount and introduced into each of the base resin and curing agent parts. is appropriate.
In addition to the thermally conductive filler, the filler component may include various types of fillers if necessary, such as carbon fillers such as graphite, fumed silica, or clay. You can also.

The resin composition may further contain necessary components in addition to the components described above.
In one example, the resin composition may further include a plasticizer. As mentioned above, in the present application it is possible to ensure low adhesion to certain materials without applying plasticizers, although small amounts of plasticizers can also be applied if necessary.

There are no particular restrictions on the types of plasticizers that can be used; for example, dioctyl phthalate (DOP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), diisononyl phthalate (d iisononyl Phthalate plasticizers such as phthalate, DINP) or polyethyleneterephthalate (PET), dioctyl adipate (DOA) or diisononyl adipate (DI) Adipate plasticizers such as NA), fatty acid plasticizers, phosphorus An acid plasticizer or a polyester plasticizer can be applied.

When a plasticizer is included, its proportion can be adjusted depending on the purpose. For example, when the plasticizer is included, the lower limit of the weight ratio of the plasticizer to 100 parts by weight of the oil-modified polyol compound is 0.5 parts by weight, 1.5 parts by weight, 2 parts by weight, 3 parts by weight. Parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight , 40 parts by weight, 45 parts by weight, 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight or about 300 parts by weight, and the upper limit thereof is 500 parts by weight, 450 parts by weight. , 400 parts by weight, 350 parts by weight, 300 parts by weight, 250 parts by weight, 200 parts by weight, 150 parts by weight, 100 parts by weight, 90 parts by weight, 80 parts by weight, 70 parts by weight, 60 parts by weight, 50 parts by weight, 40 parts by weight Parts by weight, 30 parts by weight, 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, 10 parts by weight , 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight or about 1 part by weight. Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.

In another example, when the plasticizer is included, the lower limit of the ratio of the plasticizer to 100 parts by weight of the total of the oil-modified polyol and oil-modified alcohol (oil-modified component) is 0.5 parts by weight, 1.5 parts by weight, 2 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, It may be about 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight or 140 parts by weight, and the upper limit is 400 parts by weight, 350 parts by weight, 300 parts by weight, 250 parts by weight, 200 parts by weight, 150 parts by weight, 100 parts by weight, 90 parts by weight, 80 parts by weight, 70 parts by weight, 60 parts by weight, 50 parts by weight, 40 parts by weight, 30 parts by weight, 20 parts by weight, 19 parts by weight, 18 parts by weight parts, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, It may be about 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight or 1 part by weight. Said percentage is less than or equal to any one of the above upper limits, greater than or equal to any one of the above lower limits, or any of the above lower limits. may be greater than or equal to one of the lower limits, and may be less than or equal to any one of the above upper limits.
The above ratio can also be changed in consideration of the composition of the entire resin composition and the intended use.

In addition to the above-mentioned components, the resin composition may contain further components as necessary. Examples of further components include catalysts to assist or accelerate the curing reaction, viscosity modifiers (e.g. thixotropic agents) for adjusting the viscosity, e.g. for increasing or decreasing the viscosity, or for adjusting the viscosity by shear forces. agent, diluent, etc.), a dispersant, a surface treatment agent, a coupling agent, etc.
The resin composition may further contain a flame retardant or a flame retardant auxiliary agent. In this case, known flame retardants can be used without any particular restrictions, such as solid filler flame retardants or liquid flame retardants.

Examples of the flame retardant include organic flame retardants such as melamine cyanurate and inorganic flame retardants such as magnesium hydroxide. When the amount of filler filled in the resin layer is large, a liquid type flame retardant material (TEP, triethyl phosphate, TCPP, tris (1,3-chloro-2-propyl) phosphate, etc.) may be used. Additionally, a silane coupling agent that can act as a flame retardant enhancer may be added.

The resin composition may be a one-part composition or a two-part composition, as described above. In the case of a two-component composition, the above-mentioned components of the resin composition may be contained separately in a physically separate main component part and a curing agent part.

In one example, the present application relates to a composition (two-component composition) in which the resin composition is a two-component resin composition.
Such a two-part composition may include at least a base agent part and a hardener part, and the base agent and hardener part may be physically separated from each other. When these physically separated base and curing agent parts are mixed, a curing reaction begins, resulting in the formation of polyurethane.

In the two-component composition, the base part may contain at least the hydroxyl-active component (particularly the oil-modified polyol compound), and the curing agent part may contain at least the polyisocyanate.

When the resin composition contains the above-mentioned general polyol compound, this compound may be included, for example, in the base component.
Further, the filler component may be contained in either one of the base agent and the curing agent part, or may be contained in both the base agent and the curing agent part. When the filler component is included in both the base resin and the hardener part, the base resin and the hardener part may contain the same amount of the filler component.

Other components such as catalysts, plasticizers, flame retardants, etc. may be included in the base material and/or curing agent parts as necessary.
Further, in the two-component composition, a volume ratio (P/N) of the volume (P) of the base agent part to the volume (N) of the curing agent part may be within a range of about 0.8 to 1.2. .

Such a two-component composition or its cured product also has the above-mentioned adhesion to aluminum and polyester, thermal conductivity, hardness, radius of curvature, insulation, flame retardancy, specific gravity, shrinkage rate, coefficient of thermal expansion, and/or The 5% weight loss temperature in thermogravimetric analysis (TGA) can be shown.

The present application also relates to a product containing the resin composition or a cured product thereof. The resin composition of the present application or its cured product can be usefully applied as a heat dissipation material. Accordingly, the product may include heat generating components. The term heat-generating component refers to a component that generates heat during use, and its type is not particularly limited. Typical heat-generating components include various electrical/electronic products, including battery cells, battery modules, or battery packs.

The product of the present application may include, for example, the heat-generating component and the resin composition (or the two-component composition) or a cured product thereof that is present adjacent to the heat-generating component.
The specific method of constructing the product of the present application is not particularly limited, and when the resin composition or two-component composition of the present application or a cured product thereof is applied to a heat dissipating material, the product can be formed by various known methods. Products can be configured.

In the present application, it is possible to provide a resin composition or a cured product thereof that exhibits high thermal conductivity and low adhesive strength to a predetermined adherend. Further, in the present application, the low adhesive strength can be achieved without using adhesive strength adjusting components such as plasticizers or with a minimized usage ratio thereof. The present application can also provide a product containing the curable composition or a cured product thereof.

FIG. 1 shows the analysis results for oil modification components obtained in production examples. FIG. 2 shows the analysis results for oil modification components obtained in the production example.

The present application will be specifically explained below based on Examples, but the scope of the present application is not limited by the Examples below.
The cured products mentioned below are all prepared by mixing the main ingredient and curing agent parts of the resin compositions of the examples produced in the two-component type so as to satisfy the OH/NCO equivalent ratio described in each example. It was formed by maintaining it at room temperature for about 24 hours.

1. Thermal Conductivity The thermal conductivity of the resin composition or its cured product was measured by the Hot-Dist method according to the ISO22007-2 standard. Specifically, a two-component mixture of the main agent part and the curing agent part of the example or comparative example in a volume ratio of 1:1 was placed in a mold with a thickness of approximately 7 mm, and was heated through using Hot Disk equipment. Thermal conductivity was measured in the plane direction. As stipulated in the above standard (ISO22007-2), Hot Disk equipment measures temperature changes (electrical resistance changes) by heating a sensor with a double spiral structure of nickel wire. This is equipment that can confirm conductivity, and thermal conductivity was measured according to such standards.

2. Measurement of Adhesion to Polyester Adhesion to polyester was evaluated on a test piece manufactured by attaching a PET (polyethylene terephthalate) film and an aluminum plate. As the PET film, a film with a width of about 10 mm and a length of about 200 mm was used, and as the aluminum plate, an aluminum plate with a width and a length of 100 mm was used. A test piece was prepared by coating the entire surface of the aluminum plate with a resin composition, and maintaining the PET film attached to the resin composition at room temperature (about 25° C.) for about 24 hours. At this time, about 100 mm of the entire width and length of the PET film was attached to the aluminum plate via the resin composition. The adhesive force was measured while peeling the PET film from the aluminum plate in the length direction with the aluminum plate of the test piece fixed. The above-mentioned adhesion is carried out after applying a resin composition (a mixture of a main component part and a curing agent part in a volume ratio of 1:1) to the aluminum plate so that the thickness after curing is about 2 mm, and then attaching the PET film to the above-mentioned film. The resin composition was cured by being brought into close contact with the layer of the resin composition and maintained at room temperature (about 25° C.) for about 24 hours. The peeling was performed at a peeling speed of about 0.5 mm/min and a peeling angle of 180 degrees until the PET film was completely peeled off.

3. Measurement of adhesive strength to aluminum An uncured resin composition (mixture of main component parts and curing agent parts) was placed in the center of an aluminum substrate with horizontal and vertical lengths of 2 cm and 7 cm, respectively, to a width of about 2 cm and a length of about 2 cm. Further, an aluminum substrate having horizontal and vertical lengths of 2 cm and 7 cm, respectively, was attached on the coating layer, and this state was maintained to cure the resin composition. In the above, two aluminum substrates were attached to each other at a 90 degree angle. Then, with the upper aluminum substrate fixed, the lower aluminum substrate was pressed at a speed of 0.5 mm/min to measure the force during which the lower aluminum substrate was separated, and the maximum value measured in the process was measured. Adhesion to aluminum was determined by dividing the force by the area of the test piece.

Based on the measurement results, the adhesive strength to aluminum was evaluated based on the following criteria.
<Evaluation criteria>
Top: Adhesive force to aluminum is 0.1 N/mm ² or less Middle: Adhesive force to aluminum exceeds 0.1 N/mm ² and 0.4 N/mm ² or less Bottom: Adhesive force to aluminum exceeds 0.4 N/mm ²

4. Measurement of Hardness The hardness of the cured product of the resin composition was measured according to ASTM D 2240 and JIS K 6253 standards. The initial hardness was measured using ASKER, a durometer hardness device, by applying a load of 1 kg or more (approximately 1.5 kg) to the surface of a flat sample (resin layer), and after 15 seconds, the measured value was stabilized. It was confirmed and the hardness was evaluated.

5. Measurement of radius of curvature The radius of curvature of the cured product was evaluated using cured products with width, length, and thickness of 1 cm, 10 cm, and 2 mm, respectively. The radius of curvature is the minimum radius of the cylinder at which a crack does not occur in the cured body when the cured body is attached to cylinders having various radii and bent along the longitudinal direction.

6. Measurement of Weight Average Molecular Weight The weight average molecular weight (Mw) was measured using GPC (Gel permeation chromatography). Specifically, the weight average molecular weight (Mw) is determined by placing the sample to be analyzed in a 5 mL vial, diluting it with THF (tetrahydrofuran) solvent to a concentration of approximately 1 mg/mL, and then using it as a standard sample for calibration. The analysis sample can be filtered through a syringe filter (pore size: 0.45 μm) and then measured. ChemStation from Agilent Technologies is used as an analysis program, and the weight average molecular weight (Mw) can be determined by comparing the elution time of the sample with the calibration curve.

<GPC measurement conditions>
Equipment: Agilent technologies 1200 series
Column: TL Mix. from Agilent technologies. A&B used Solvent: THF (tetrahydrofuran)
Column temperature: 35℃
Sample concentration: 1 mg/mL, 200 μl injection Standard sample: Polystyrene (MP: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485) used

Manufacturing example 1.
Production example 1A.
A mixture of an oil-modified polyol compound represented by the following chemical formula A and an oil-modified polyol compound represented by the following chemical formula B was manufactured in the following manner.

Trimethylolpropane and linoleic acid, which is an unsaturated fatty acid, were mixed in a flask at a weight ratio of about 1:3.48 (trimethylolpropane:linoleic acid). A catalyst (Tin (II) 2-ethylhexanoate (Sigma-Aldrich)) was added to the mixture in an amount of about 0.5 parts by weight based on 100 parts by weight of the whole, and the mixture was heated at 150°C under inert gas purge conditions. Stirring was maintained for 30 minutes. Next, a small amount of xylene, which is an azeotropic solution, was added, the temperature was raised to 190° C., the reaction was carried out for 15 hours or more, and the pressure was reduced to 40 Torr or less for 2 hours or more to remove xylene and unreacted substances. After cooling the reaction mixture, it was filtered through a filter to obtain the desired product.

From the GPC analysis results of the obtained target product, it can be confirmed that the oil-modified polyols of the chemical formulas A and B are present in the target product at a weight ratio of about 1:2 (A:B). Ta.
The weight average molecular weight of the target product, which was confirmed through GPC analysis, was about 1307 g/mol.

Production example 1B.
Same as Production Example 1B except that when mixing trimethylolpropane and linoleic acid, which is an unsaturated fatty acid, the weight ratio (trimethylolpropane:linoleic acid) was about 1:3.34. The target product was synthesized.
From the GPC analysis results of the obtained target product, it is confirmed that the oil-modified polyols of the chemical formulas A and B are present in the target product at a weight ratio of about 1:1.5 (A:B). was completed.
The weight average molecular weight of the target product, which was confirmed through GPC analysis, was about 1268 g/mol.

Production example 1C.
Same as Production Example 1B except that when mixing trimethylolpropane and linoleic acid, which is an unsaturated fatty acid, the weight ratio (trimethylolpropane:linoleic acid) was about 1:3.14. The target product was synthesized.
From the GPC analysis results of the obtained target product, it can be confirmed that the oil-modified polyols of the chemical formulas A and B are present in the target product at a weight ratio of about 1:1 (A:B). Ta.
The weight average molecular weight of the target product, which was confirmed through GPC analysis, was about 1210 g/mol.

Production example 1D.
Same as Production Example 1B except that when mixing trimethylolpropane and linoleic acid, which is an unsaturated fatty acid, the weight ratio (trimethylolpropane:linoleic acid) was about 1:2.79. The target product was synthesized.
From the GPC analysis results of the obtained target product, it can be confirmed that the oil-modified polyols of the chemical formulas A and B are present in the target product at a weight ratio of about 2:1 (A:B). Ta.
The weight average molecular weight of the target product, which was confirmed through GPC analysis, was about 1113 g/mol.
FIG. 1 shows the GPC analysis results for Production Example 1D.

Production example 2.
A mixture of an oil-modified polyol represented by the following chemical formula C and an oil-modified alcohol represented by the chemical formula D was manufactured in the following manner.

In the chemical formula C, each n is about 4, R ₁ is a substituent of the following chemical formula C-1, and R ₂ is a substituent of the following chemical formula C-2.

In the chemical formula D, each n is about 4, R ₁ is a substituent of the following chemical formula C-1, and R ₂ is a substituent of the following chemical formula C-2.

In chemical formula C-1, n is about 4.

In chemical formula C-2, the * symbol means that the moiety is linked to chemical formula C or D.
A compound of the following chemical formula E (PPG, manufacturer: Perstorp, product name: Polyol 3380) and linoleic acid, an unsaturated fatty acid, were mixed in a flask at a weight ratio of 1:0.83 (compound of chemical formula E: linoleic acid). did.

In the chemical formula E, each n is about 4, and R ₁ is a substituent of the following chemical formula E-1.

In chemical formula E-1, n is about 4.
After adding a catalyst (Tin(II) 2-ethylhexanoate (Sigma-Aldrich)) to the mixture in an amount of about 0.5 parts by weight based on 100 parts by weight of the entire mixture, under inert gas purge conditions, Stirred and maintained at 150° C. for 30 minutes. Next, a small amount of xylene, which is an azeotropic solution, was added, the temperature was raised to 190° C., the reaction was carried out for 6 hours or more, and the pressure was reduced to 40 Torr or less for 1 hour or more to remove xylene and unreacted substances. Next, the reaction product was cooled and filtered through a filter to obtain the desired product.

As a result of GPC analysis of the obtained target product, a polyol compound of chemical formula C and an alcohol compound of chemical formula D were present in the target product at a weight ratio of about 25:75 (C:D).
Further, as a result of GPC analysis, the weight average molecular weight of the polyol compound of chemical formula C in the target object is about 600 g/mol level, the weight average molecular weight of the compound of chemical formula D is about 2000 g/mol level, and the mixture The weight average molecular weight of (target product) was approximately 1263 g/mol.
FIG. 2 shows the GPC analysis results for the target object.

Example 1.
Production of base parts The target product obtained in Production Example 1B, a general polyol (Perstorp, Capa 3091), and a filler component are mixed at a weight ratio of 10.5:1.5:88 (Production Example 1: general polyol: filler component). Then, the base material parts were manufactured. In the above, the filler component was produced by mixing a first alumina filler with an average particle size of about 70 μm, a second alumina filler with an average particle size of about 20 μm, and a third alumina filler with an average particle size of about 1 μm. The weight ratio during the mixing was approximately 6:2:2 (first alumina filler: second alumina filler: third alumina filler).

Hardener Part Production Polyisocyanate (Vencorex, Tolonate HDT-LV2) was used as a hardener. The polyisocyanate and filler component were mixed at a weight ratio of 10:90 (polyisocyanate:filler component) to produce a hardener part. In the above, the same filler component as the base part was used.

Production of resin composition A resin composition (curable composition) was prepared by preparing the main component part and the curing agent part, and after mixing the main component and the curing agent part, the mixture was maintained at room temperature to form a cured product. In the above mixing, the equivalent ratio (OH/NCO) of the hydroxy group (OH) present in the base agent part and the isocyanate group (NCO) present in the curing agent part was about 180.

Example 2.
A resin composition (curable composition) was prepared by preparing a base resin part and a curing agent part in the same manner as in Example 1, and after mixing the base resin and curing agent part, the resin composition was maintained at room temperature to form a cured body. , and the mixture was made such that the equivalent ratio (OH/NCO) of the hydroxy groups (OH) present in the base agent part and the isocyanate groups (NCO) present in the curing agent part was about 260.

Example 3.
Production of main component parts The target product obtained in Production Example 1B, the first general polyol (Perstorp, Capa 2043), the second general polyol (Perstorp, Capa 3091), and the filler components were mixed in a ratio of 10.5:0.5:0. A base part was manufactured by mixing at a weight ratio of 5:88.5 (Manufacturing Example 1B: first general polyol: second general polyol: filler component). The same filler components as in Example 1 were used.

Hardener Part Production Polyisocyanate (Vencorex, Tolonate HDT-LV2) was used as a hardener. The polyisocyanate and filler component were mixed at a weight ratio of 10:90 (polyisocyanate:filler component) to produce a hardener part. The same filler component as in Example 1 was used.

Production of resin composition A resin composition (curable composition) was prepared by preparing the base resin part and the curing agent part, and after mixing the base resin and the curing agent part, the mixture was maintained at room temperature to form a cured product. In the above mixing, the equivalent ratio (OH/NCO) of the hydroxy group (OH) present in the base agent part and the isocyanate group (NCO) present in the curing agent part was about 180.

Example 4.
Production of base parts The target product of Production Example 1C, general polyol (Perstorp, Capa 3091), and filler component are mixed at a weight ratio of 11.2:0.6:88.2 (Production Example 1C: general polyol: filler component). Then, the base material parts were manufactured. In the above, the same filler components as in Example 1 were used.

Hardener Part Production Polyisocyanate (Vencorex, Tolonate HDT-LV2) was used as a hardener. The polyisocyanate and filler component were mixed at a weight ratio of 10:90 (polyisocyanate:filler component) to produce a hardener part. In the above, the same filler components as in Example 1 were used.

Production of resin composition A resin composition (curable composition) was prepared by preparing the base resin part and the curing agent part, and after mixing the base resin and the curing agent part, the mixture was maintained at room temperature to form a cured product. In the above mixing, the equivalent ratio (OH/NCO) of the hydroxy group (OH) present in the base agent part and the isocyanate group (NCO) present in the curing agent part was about 260.

Example 5.
Production of main component parts The target product of Production Example 1B, the first general polyol (Perstorp, Capa 2043), the second general polyol (Perstorp, Capa 3091), and the filler components were mixed into 8.1:2.9:0.6: A base part was manufactured by mixing at a weight ratio of 88.4 (Manufacturing Example 1B: first general polyol: second general polyol: filler component). In the above, the same filler components as in Example 1 were used.

Hardener Part Production Polyisocyanate (Vencorex, Tolonate HDT-LV2) was used as a hardener. The polyisocyanate and filler component were mixed at a weight ratio of 10:90 (polyisocyanate:filler component) to produce a hardener part. In the above, the same filler components as in Example 1 were used.

Production of resin composition A resin composition (curable composition) was prepared by preparing the base resin part and the curing agent part, and after mixing the base resin and the curing agent part, the mixture was maintained at room temperature to form a cured product. In the above mixing, the equivalent ratio (OH/NCO) of the hydroxy group (OH) present in the base agent part and the isocyanate group (NCO) present in the curing agent part was about 220.

Example 6.
Production of base material parts The target material of Production Example 2, a plasticizer (diisononyl adipate, DINA), and a filler component are mixed at a weight ratio of 6:6:88 (Production Example 2: plasticizer: filler component) to form a base material part. Manufactured. In the above, the same filler components as in Example 1 were used.

Hardener Part Production Polyisocyanate (Vencorex, Tolonate HDT-LV2) was used as a hardener. The polyisocyanate and filler component were mixed at a weight ratio of 10:90 (polyisocyanate:filler component) to produce a hardener part. In the above, the same filler components as in Example 1 were used.

Production of resin composition A resin composition (curable composition) was prepared by preparing the base resin part and the curing agent part, and after mixing the base resin and the curing agent part, the mixture was maintained at room temperature to form a cured product. In the above mixing, the equivalent ratio (OH/NCO) of the hydroxy group (OH) present in the base agent part and the isocyanate group (NCO) present in the curing agent part was about 100.

Example 7.
When manufacturing the base material part, the target material of Production Example 1B is used instead of the target material of Production Example 1C, and the mixture of the base material and the curing agent part is mixed with the hydroxy group (OH) present in the base material part and the curing agent part. A resin composition was produced in the same manner as in Example 2, except that the equivalent ratio (OH/NCO) of isocyanate groups (NCO) present in the resin part was about 260.
The results of physical property evaluation organized for each of the above examples are shown in Table 1 below.

Claims (18)

Contains polyol components and fillers,
A curable composition that forms a cured product having an adhesive strength of 100 gf/cm or less to a polyester surface. The curable composition according to claim 1, which forms a cured product having an adhesive strength to aluminum of 0.1 N/mm ² or less. The curable composition according to claim 1, which forms a cured product having a Shore OO hardness of 95 or less. The curable composition according to claim 1, wherein the polyol component includes a polyol compound containing at least one linear or branched hydrocarbon group having 3 or more carbon atoms at the end. The curable composition according to claim 1, wherein the polyol component includes a polyol compound containing at least one terminal substituent represented by the following chemical formula 1:
In Chemical Formula 1, R is a straight chain or branched hydrocarbon group having 3 or more carbon atoms. The curable composition according to claim 4 or 5, wherein the polyol compound has a polyester skeleton or a polyether skeleton. The curable composition according to claim 4 or 5, wherein the polyol compound has a polycaprolactone skeleton or a polyalkylene skeleton. The curable composition according to claim 1, wherein the polyol component includes a polyol compound having a weight average molecular weight within the range of 100 g/mol to 5000 g/mol. 2. The curable composition of claim 1, further comprising a compound containing a linear or branched hydrocarbon group having three or more carbon atoms and one hydroxy. The curable composition according to claim 1, further comprising a polyol having no linear or branched hydrocarbon groups having 3 or more carbon atoms. The curable composition according to claim 10, wherein the polyol having no linear or branched hydrocarbon group having 3 or more carbon atoms has a weight average molecular weight within the range of 100 g/mol to 5,000 g/mol. thing. The curable composition according to claim 10, wherein the polyol having no linear or branched hydrocarbon group having 3 or more carbon atoms is a polyfunctional polyol having difunctionality or more. The curable polyol according to claim 10, wherein the polyol having no linear or branched hydrocarbon group having 3 or more carbon atoms is a polycaprolactone polyol or a polyol having an alkanediol unit, a polyol unit, and a dicarboxylic acid unit. Composition. The curable composition according to claim 1, further comprising a polyisocyanate. The curable composition of claim 1, further comprising a plasticizer. Hardening according to claim 1, wherein the filler is aluminum hydroxide, magnesium hydroxide, calcium hydroxide, hydromagnesite, magnesia, alumina, aluminum nitride, boron nitride, silicon nitride, silicon carbide, zinc oxide or beryllium oxide. sexual composition. A base part containing a polyol component and a filler,
a hardener part including a hardener component and a filler;
A two-component composition that forms a cured product with an adhesive strength of 100 gf/cm or less to a polyester surface. A product comprising a heat generating component and a cured product of the curable composition according to any one of claims 1 to 16 or the two-component composition according to claim 17, which is present adjacent to the heat generating component.